Nitroso aryloxy quaternary ammonium compounds

ABSTRACT

1. A COMPOUND OF THE FORMULA   (Q)+ (O-AR-NO-)-   IN WHICH THE -O-AR-NO- MOIETY IS SELECTED FROM THE GROUP CONSISTING OF P-NITROSO PHENATE IN WHICH AR IS P-PHENYLENE, AND P-NITROSO NAPHTHENATE IN WHICH AR IS NAPHTHALENE; AND THE Q MOIETY IS SELECTED FROM THE GROUP CONSISTING OF: DODECYL DIMETHYL BENZYL AMMONIUM; DODECYL BENZYL ISOQUINOLINIUM; MYRISTYL METHYL PYRROLIDINIUM; COCO METHYL PYRROLIDINIUM; LAURYL ETHYL PIPERIDINIUM; 1-(3,4 - DICHLOROBENZYL) - 1 - HYDROXYETHYL - 2 - STEARYL IMIDAZOLINIUM; LAURYL ALPHA PICOLINIUM; LAURYL TRIMETHYL AMMONIUM; AND COCO METHYL MORPHOLINIUM GROUPS WHERE AR IS A P-PHENYLENE GROUP; AND COCO DIMETHYL BENZYL AMMONIUM WHEN AR IS NAPHTHALENE.

United States Patent Int. Cl. C07d 87/32 US. Cl. 260247.7 C 11 Claims ABSTRACT OF THE DISCLOSURE Nitroso aryloxy quaternary ammonium compounds, containing a nitroso substituent, oxidizable to N or reducible to NH in appropriate liquid media is used to control reductive or oxidative potential of the medium.

REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of Ser. No. 119,350 filed Feb. 26, 1971, which application is a continuation-in-part of Ser. No. 659,321, filed Aug. 9, 1967 and now abandoned.

BACKGROUND OF THE INVENTION This invention relates generally to new compositions of matter and particularly to such compositions which contain a quaternary ammonium moiety. The new compositions have been found to be surprisingly effective in biocidal applications including use as fungicides, bactericides and slimicides and in other applications where control of micro-organisms, directly or through modification of their environment, is desired. Such applications will include, particularly, amelioration of raw sewage by selective destruction of noxious vapor generating organisms such as the Desulfovibrio desulfurz'cans.

' The invention is particularly concerned with improved performance of known ammonium radicals through the simultaneous control of the oxidative or reductive condition of the medium in which the radical is to operate. In certain embodiments, the present compounds afford simultaneous control of microbiological and oxidative phenomena, e.g. by destroying microbes and inhibiting rust simultaneously in applications demanding such joint benefits, for example, secondary oil recovery operations.

The invention further is concerned with methods for the in situ generation of NH and N0 substituents in aryloxy quaternary ammonium compound solutions and resultant control of the oxidative or reductive state of such solutions.

Prior Art Quaternary ammonium compounds are well known. The biologic properties of quaternary ammonium compounds are similarly well known. To my knowledge, however, a nitroso aryloxy moiety has not previously been combined with a quaternary ammonium moiety to form an ionically bonded compound. Nor has it been recognized heretofore that such combination provides a means of closely controlling the oxidative or reductive state of an ammonium containing solution made therefrom to thus enable maximum biological activity from the ammonium radical.

SUMMARY OF THE INVENTION There have been discovered compounds having the formula [Q] [OArNO] 3,842,079 Patented Oct. 15, 1974 is an aryl group. These compounds have been found to exhibit the bactericidal, fungicidal and antiseptic qualities of the ammonium moiety to an increased degree, and to have the property of lessening the reducing or oxidizing propensities of the medium in which the compound is disclosed, thus to increase the biocidal eliectiveness of the ammonium moiety. i

A typical preparation of these new compounds is carried out as follows: All parts are by Weight. To one molar part of dodecyldimethyl amine dissolved in methyl alcohol there is added one molar part of benzyl chloride and the mixture is refluxed for 24 hours. The resultant dodecyl dimethyl benzyl ammonium chloride is mixed with an alcoholic solution containing one molar part sodium metal and one molar part phenol and the m'urture heated to 50 C. for 15 minutes. Following cooling to room temperature and filtering off of precipitated sodium chloride, the filtrate, an alcoholic solution of dodecyl dimethyl benzyl ammonium phenate is saturated with nitrous oxide gas and let stand for 24 hours. A waxy solid is obtained on evaporative removal of the alcohol: dodecyl dimethyl benzyl ammonium nitroso phenate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The ammonium moiety of the present compound is conventional in structure and is similarly effective biocidally with increased efficiency by virtue of the remainder of the compound molecule, the -O--Ar-NO moiety. This moiety is a nitroso aryloxy and may contain an Ar group which is dinuclear, e.g. naphthyl or mononuclear, e.g. phenyl, tolyl, ethylbenzyl, cumyl, resorcyl groups or the like having the O and NO substituents in the ortho or para arrangement. Preferred compounds have p-phenylene radicals as the Ar group and contain up to 2 other substituents selected from hydroxy, chlorine and bromine groups and alkyl groups having from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl and isobutyl groups.

The compounds of the present invention may be made by the reaction of a quaternary ammonium halide and an alkali metal ester of the aryl alcohol desired, e.g. sodium phenate, separating the resultant ammonium phenate and by-product salt and reacting with nitrous oxide gas to substitute the nitroso group onto the aromatic ring. Reaction conditions are mild throughout, e.g. room temperature or slightly above and alcoholic media is conveniently used.

EXAMPLES (All parts by Weight) A. Preparation of the Compounds 1. Two and three-tenths parts of sodium metal was dissolved in parts of methyl alcohol. To the solution 9.4 parts of phenol was added and on its dissolution 326 parts of coco dimethyl benzyl ammonium chloride was added. After mixing and heating for 15 minutes at 50 C. the solution was cooled to 24 C. and filtered to separate the sodium chloride produced. The filtrate containing coco dimethyl benzyl ammonium phenoxide in alcohol solution is saturated with nitrous oxide using a sparging tube. Reaction to the nitroso phenate occurs over a 24 hour period at room temperature. The alcohol is evaporated otf leaving a waxy solid, coco dimethyl benzyl ammonium p-nitroso phenate.

2. Example A-1 is duplicated substituting 10.8 parts of cresol for the phenol. There is obtained a waxy solid, coco dimethyl benzyl ammonium p-nitroso cresate.

3. Example A-l is duplicated utilizing dodecyl dimethyl benzyl ammonium chloride prepared from 21.3 parts of dodecyldimethyl amine and 12.65 parts of benzyl chloride in methyl alcohol solution by reflux for 24 hours. A waxy solid, dodecyl dimethyl benzyl ammonium p-nitroso phenate is obtained.

4. Example A-1 is duplicated substituting an equivalent molar amount of lauryl trimethyl ammonium chloride for the chloride used there. The product obtained is lauryl trimethyl ammonium p-nitroso phenate.

5. Example A-'l is duplicated substituting an equivalent molar amount of dodecylbenzyl isoquinolinium chloride for the ammonium chloride. The product obtained is dodecyl benzyl isoquinolinium p-nitroso phenate.

6. Example A-2 is duplicated substituting an equivalent molar amount of myristyl methyl pyrrolidinium chloride for the ammonium chloride. The product obtained is myristyl methyl pyrrolidinium p-nitroso phenate.

7. Example A-l is duplicated substituting an equivalent molar amount of lauryl ethyl piperidinium chloride for the ammonium chloride. The product obtained is lauryl ethyl piperidinium p-nitroso phen ate.

8. Example A-1 is duplicated substituting an equivalent molar amount of coco methyl pyrrolidinium chloride for the ammonium chloride. The product is coco methyl pyrrolidinium p-nitroso phenate.

9. Example A-l is duplicated substituting an equivalent molar amount of 1-(3,4-dichlorobenzyl)-l-hydroxyethyl- 2-stearyl imidazolinium chloride for the ammonium chloride. The product is l-(3,4-dichlorobenzyl)-l-hydroxyethyl-2-stearyl imidazolinium p-nitroso phenate.

10. Example A-l is duplicated substituting an equivalent molar amount of lauryl alpha picolinium chloride for the ammonium chloride. The product obtained is lauryl alpha picolinium p-nitroso phenate.

11. Example A-l is duplicated substituting an equivalent amount of coco methyl morpholinium chloride for the ammonium chloride. The product obtained is coco methyl morpholinium p-nitroso phenate.

12. Example A-l is duplicated substituting an equivalent molar amount of naphthol for the phenol. The product obtained is coco dimethyl benzyl ammonium p-nitroso naphthenate.

B. Bacteriocidal Properties Compounds for Examples A1 to A-l2 are tested for bacteriocidal and bacteriostatic effectiveness. Results are interpreted as the lowest effective concentration (=highest dilution) being best. In each test trypticase soya bacteriological medium was placed in test tubes in 5 milliliter amounts. To a series of such tubes each compound A-l through A-12 was added in amounts ranging from 1 to 500 parts per million (p.p.m.). The treated tubes were inoculated with various microorganisms and allowed to incubate 24 hours at 37.5 C.

At the end of the incubation period, a reading is taken of growth or no growth, tubes showing growth are discarded. The highest dilution at which no growth occurs is the bacteriostatic concentration; tubes which show no growth are subcultured into fresh media and allowed to incubate at 37.5 C. for an additional 48 hours. Again tubes showing positive growth are discarded. The highest dilution at which no growth occurs is the bacteriocidal concentration. Results typical of each of the A1 through A-12 compounds against various microorganisms is given below in Table I.

These compounds are seen to be highly elfective at notably low levels, particularly against the pseudomonad microorganisms.

C. Fungicidal Properties The technique and materials of Example B are used substituting Saborouds liquid medium for fungi as the medium. Typical results for Compounds A-l through A-l2 are given in Table II.

R/tizopus 'nz'griftcans Pcm'cillimn lutcum D. Sewage Amelioration The compound coco dimethyl benzyl ammonium p-nitroso phenate (A-l) is particularly effective against biological generation of hydrogen sulfide gas. Other compounds A-2 through A-l2 may be expected to be similarly effective. Compound A-l was evaluated for sewage amelioration properties by treating raw sewage (D-l), aeration tank outfall (DZ), digestion tank outfall (D-3) and clear effluent reclaim water (D-4) by adding compound (A-1) to the various samples (Dl to D4) to which had been added trypticase soya bacteriological media. The cultures were incubated seven days at 37.5 C. At the end of the incubation period the cultures were examined for growth of the microbe Desulfovibro desulfuricans and for the odor of H 5 gas. Results were as follows:

D1Raw sewage water samplel.0 p.p.m. prevented the growth of Desulfovibrio desulfuricans with no hydrogen sulfide gas being produced.

D2Water sample from aeration tank1.0 p.p.m. was bacteriostatic for Desulfovibrio desulfuricans with no hydrogen sulfide gas being produced.

D-3-Water sample from digestion tank0.5 p.p.m. prevented growth of Desulfovibrio desulfuricans with no hydrogen sulfide gas being produced.

D4Clear effluent water.5 p.p.m. prevented growth of Desulfovibrio desulfuricans with no hydrogen sulfide gas being produced.

It is noteworthy that aerobic digestion was continued in the presence of the bacteriocide showing a high selectivity for the undesired pseudomonad.

E. Rust Inhibition and Removal Compounds A-l through A-12 are tested for rust inhibiting capabilities. Each compound is diluted to concentrations between 50 and 500 p.p.m. in water and flushed through rusted iron pipe several times with dwell times ranging up to several hours. Rust removal is effected in each instance, with those compounds having detergent like radicals, e.g. Compound A-l, showing excellent results due to more etficient loosening of adherent scaler rust. Comparative tests for rust inhibition are also carried out with the result of no corrosion in the case of water standing in the pipe section with dissolved amounts Compounds A-l to A-12 between 50 and 500 p.p.m. after several months and quite apparent rust in ordinary water containing pipe sections. It is believed the present compounds may effectively compete for oxidizers in the water, e.g. dissolved oxygen converting the nitroso group by oxidation to N0 which of course is a known rust inhibitor in the NaNO form.

F. Secondary Oil Recovery It will be evident that in combining the properties of rust inhibition and suppression of H 8 generation the present compounds are ideal additives for brine or other aqueous fluid used to recover additional oil from wells following conventional drilling extraction. This process is Well known as the use of various anti-bacterial and anti-corrosive additives, particularly in sour gas fields such as those in Texas. See for example US. Pat. 2,7 33,- 206 to Prusick and US. Pat. 2,472,400 to Bond et al.

Testing of compounds A-2 through A-12 shows that H S generation is suppressed as the reducing state of the oil-brine mixture is lessened by reductive conversion of the -NO group to NH and the Desulfovibrio desulfuricans are accordingly destroyed and produce no H 8. Simultaneously the NO group at surfaces subject to oxidative attack from dissolved oxygen in the recovery fluid are protected by the preferential oxidation of the -NO group to --NO In addition slime formation is prevented and fouling of lines, pumps and filters is materially reduced. Use concentrations will range between 0.5 and 1000 p.p.m. or higher up to 10,000 p.p.m. for secondary oil recovery solutions.

G. Surface Fungicide The compounds A-l through A-l2 are incorporated in various hydraulic materials such as concrete and plaster in concentrations up to 1000 p.p.m. Growth of fungi is inhibited at the surfaces of the formed material. Similarly coating material such as water latex paints may be treated to resist fungi by incorporation of 50 to 1500 p.p.m. of one of the present compounds.

H. Detergency As mentioned hereinabove, those compounds containing fatty acid radicals of known detergent utility retain this property in their present structures so that lard or grease may be effectively removed during biocidal use of these compounds, suggesting use of these compounds as disinfecting additives for cleaning materials, e.g. at concentrations of l to 25% by weight.

1. Controls 1. Coco dimethyl benzyl ammonium chloride was tested in the B test series above. Bacteriostatic and bacteriocidal levels were above 100 p.p.m. demonstrating the advantage conferred by addition of the nitrosophenate moiety with the quaternary ammonium moiety.

2. Nitrosophenol was tested in the B test series above. Bacteriostatic and bacteriocidal levels were not measurable in the test series, demonstrating the surprising nature of biocidal improvement by virtue of addition of a nitrosophenoxy radical to a quaternary ammonium compound.

I claim:

1. A compound of the formula in which the O-ArNO- moiety is selected from the group consisting of p-nitroso phenate in which Ar is p-phenylene, and p-nitroso naphthenate in which Ar is naphthalene; and the Q moiety is selected from the group consisting of:

dodecyl dimethyl benzyl ammonium;

dodecyl benzyl isoquinolinium;

myristyl methyl pyrrolidinium;

coco methyl pyrrolidinium;

lauryl ethyl piperidinium;

l-(3,4 dichlorobenzyl) 1 hydroxyethyl 2 stearyl imidazolinium;

lauryl alpha picolinium;

lauryl trimethyl ammonium; and

coco methyl morpholinium groups where Ar is a p-phenylene group; and

coco dimethyl benzyl ammonium when Ar is naphthalene.

2. Compound according to claim 1 in which said compound is dodecyl dimethyl benzyl ammonium p-nitroso phenate.

3. Compound according to claim 1 in which said compound is dodecyl benzyl isoquinolinium p-nitroso phenate.

4. Compound according to claim 1 in which said compound is myristyl methyl pyrrolidinium p-nitroso phenate.

5. Compound according to claim 1 in which said compound is lauryl ethyl piperidinium p-nitroso phenate.

6. Compound according to claim 1 in which said compound is coco methyl pyrrolidinium p-nitroso phenate.

7. Compound according to claim 1 in which said compound is 1-(3,4-dichlorobenzyl)-l-hydroxyethyl-2-steary1 imidazolinium p-nitroso phenate.

8. Compound according to claim 1 in which said compound is lauryl alpha picolinium p-nitroso phenate.

9. Compound according to claim 1 in which said compound is coco methyl morpholinium p-nitroso phenate.

10. Compound according to claim 1 in which said compound is coco dimethyl benzyl ammonium p-nitroso naphthenate.

11. Compound according to claim 1 in which said compound is lauryl trimethyl ammonium p-nitroso phenate.

References Cited FOREIGN PATENTS 12/1948 Great Britain.

DONALD G. DAUS, Primary Examiner J. TOVAR, Assistant Examiner US. Cl. X.R. 

1. A COMPOUND OF THE FORMULA 